FR2694288A1 - Phenylbenzamide fungicides and processes for their preparation - Google Patents

Abstract

1) Compounds of the phenylbenzamide family. 2) They are of formula (I): in which: - R1 and R2, which are identical or different, are a hydrogen or halogen atom or an optionally halogenated alkyl radical, and - R3 and R4, which are identical or different, are an alkyl containing 1 to 4 carbon atoms or can form, together with the nitrogen atom which carries them, a morpholino ring. 3) Fungicides applicable in agriculture.

Description

Phenvlbenzamides fungicides and processes for their preparation.

  The present invention relates to novel phenylbenzamide derivatives, their preparation and their use in compositions

  fungicides for the protection of plants against fungal diseases.

  European Application No. 360701 describes a very large number of amide derivatives and especially phenylbenzamides and their use.

  as an active ingredient for the control of fungal plant diseases.

  The examples show in particular their preventive activity against

diseases such as mildew.

  The Applicant has now discovered that a narrow selection of these derivatives have the properties already described but moreover, and surprisingly, such an activity at an excellent level as well as an activity

remarkable curative.

  More specifically, the invention relates to phenylbenzamide derivatives of formula (I):

R 3 N / R 4

N O

R 2 <OCH 3

R 1 O CH 3

  In which: R 1 and R 2, which may be identical or different, are a hydrogen or halogen atom or an optionally halogenated alkyl radical, and -R 3 and R 4, which may be identical or different, are an alkyl of 1 to 4 atoms of carbon, or can form, together with the nitrogen atom that carries them, a

morpholino cycle.

  The preparation of these compounds can be carried out according to the process

  described in the application cited above.

  It can be carried out according to two other processes: According to a first method, the compounds of formula (I) are prepared from the compounds of formula (I) described below, after activation of the acid function by an activating agent, preferably selected from the group consisting of thionyl chloride, phosphoryl chloride, phosphorus trichloride or pentachloride, dicyclohexylcarbodiimide, diimidazole carbonyl, alkyl chloroformates and trifluoroacetic anhydride and then reaction with amine HNR 1 R 2 in the presence of an organic or inorganic base in an organic solvent preferably selected from the group consisting of

  chlorinated or aromatic solvents or an ether such as THF.

  The compounds of formula (Im) may be prepared by saponification of the compounds of formula (I) described below. The reaction is carried out in an alcohol such as ethanol in the presence of water and a mineral base such as preferably potassium hydroxide or sodium hydroxide, at a temperature between room temperature and the reflux of the reaction mixture. The reaction mixture is then treated with an organic or inorganic acid such as

  preferably hydrochloric acid to yield the compound of formula (1 I).

  The preparation of the compounds of formula (II) can be carried out by

  an aryl coupling reaction between a compound of formula (IV) described below.

  after and 3,4-dimethoxyphenylboronic acid in the presence of a catalyst.

  To ensure good regioselectivity, it is understood that none of the other substituent atoms R 1 or R 2 can be simultaneously a bromine atom or

diode.

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  3,4-dimethoxyphenylboronic acid was prepared by

  analogy with the methods described in the literature (Organic Synthesis coll.

  vol 4 page 68 or in Journal of Organic Chemistry 49 p 5237-5243.

  The esters of formula (IV) are obtained by esterification of the acids of general formula (V) described below. The reaction is carried out in an aliphatic alcohol such as methanol or ethanol in the presence of amounts varying from 1 at 20% of a mineral acid, such as gaseous hydrochloric acid or concentrated sulfuric acid, generally at reflux of the reaction mixture. The product is then isolated by precipitation in water or extraction with a

organic solvent.

  The acids of general formula (V) are obtained by diazotization

  corresponding anthranilic acids of general formula (VI) described below.

after, according to known methods.

  The preparation of the anthranilic acids of formula (VI) is

  abundantly described in the literature.

  In a second process, the compounds of formula (I) are prepared from the compounds of formula (VII) described below, by coupling with 3,4-dimethoxyphenylboronic acid by a method similar in all respects to that described. above to pass compounds of formula (IV) to

compounds of formula (III).

  The compounds of formula (VII) are prepared from compounds of formula (V) by a method similar in all respects to that described above to pass compounds of formula (II) to compounds of formula (). The preparation of compounds of formula (V) from anthranilic acids of general formula (VI) is described above in the first method.

FORMULAS FIRST

PROCESS

  H 3 Formula I Formula II Formula 111 OR RO R 2 Br R 1 H 3 Formula IV OH Formula V Formula Vl OCH 3

FORMULAS SECOND METHOD

NR 3 R 4

  Formula I) CH 3 Formula VII Formula V R 1 Formula VI OH

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  Example 1 N, N-diethyl-2- (3,4-dimethoxyphenyl) -4-trifluoromethyl

  benzamide (compound n 1) (Formula I with R 1 = H, R 2 = CF 3, R 3 = R 4 = C 2 H 5).

  In a 1000 ml flask, 500 ml of

  dichloroethane, 60 g (0.184 mol) of 2- (3,4-dimethoxyphenyl) -4-

  trifluoromethyl benzole and 5 ml of N, N-dimethylformamide With stirring and cooling to 0 ° C, 20 ml of thionyl chloride (0.276 mol) are then added dropwise. When the addition is complete, the reaction mixture is gradually heated to 55 ° C. C. for 2 hours and then evaporated to dryness. The residue is taken up in 200 ml of tetrahydrofuran and then poured dropwise into a solution containing 58 ml (0.55 mol) of diethylamine in 200 ml of tetrahydrofuran maintained at a temperature below 10 ° C. When the addition is complete, the reaction mixture is stirred at ambient temperature for one hour and then evaporated to dryness. The residue is taken up in dichloromethane, washed successively with 1N HCl and with distilled water. After drying over magnesium sulphate, the phase organic is evaporated under

  reduced pressure to provide 62.3 g (yield: 89%) of N, N-diethyl-2-

  dimethoxyphenyl) -4-trifluoromethylbenzamide as a white solid

melting at 109-110 C.

  The following two compounds were prepared analogously:

  2- (3,4-Dimethoxyphenyl) -4-trifluoromethyl-1-

  morpholinocarbonylbenzene: 60 g (82.5%) melting at 130 ° C. (compound 2)

  (Formula I with RI = H, R 2 = CF 3, R 3 + R 4 = morpholino).

  N-ethyl-N-methyl-2- (3,4-dimethoxyphenyl) -4-trifluoromethylbenzamide: 71.2 g (81%), mp 103 ° -104 ° C. (compound No. 3) (Formula I with

  R 1 = H, R 2 = CF 3, R 3 = CH 3, R 4 = C 2 H 5).

  Example 2 2- (3,4-Dimethoxyphenyl) -4-trifluoromethylbenzoic acid (Formula II with

R 1 = H, R 2 = CF 3).

  In a two-liter flask, one successively introduced 1000 ml

  of absolute ethanol, 290 g (0.82 mol) of 2- (3,4-dimethoxyphenyl) -4-

  ethyl trifluoromethylbenzoate and 170 ml (0.164 mol) of 10N sodium hydroxide solution. The reaction mixture is refluxed for two hours and then evaporated to dryness under reduced pressure. The residue is taken up in 2.5 liters of water and extracted successively. 500 ml of ethyl acetate and 500 ml of pentane are added to the aqueous phase. 500 g of crushed ice are then added and then treated with an excess of concentrated hydrochloric acid. The precipitate that forms is filtered off on sintered glass and then

  dried under a stream of air; 240.5 g (yield: 90%) of 2-

  (3,4-dimethoxyphenyl) -4-trifluoromethylbenzoic acid as a solid

light beige melting at 194 C.

  Example 3 2- (3,4-dimethoxyphenyl) -4-trifluoromethyl benzoate

  of ethyl (formula III with R1 = H, R2 = CF3, R3 = CH3, R4 = C2H5).

  In a four-liter flask, under an inert atmosphere, 263 g (0.885 mol) of ethyl 2-bromo-4-trifluoromethylbenzoate, 750 ml of 1,2-dimethoxyethane, 4 g of tetrakistriphenylphosphine palladium, 177 g are introduced successively ( 0.974 mol) of 3,4-dimethoxyphenylboronic acid and 1000 ml of a 2M aqueous sodium carbonate solution. The reaction mixture is refluxed for 14 hours and then evaporated to a third under reduced pressure. The reaction mixture is poured over two liters. water; the precipitate that forms is filtered on sintered glass, rinsed with water and then dried under a stream of air.

  obtains 294 g (yield: 94%) of 2- (3,4-dimethoxyphenyl) -4-

  ethyl trifluoromethyl benzoate in the form of a beige solid melting at 89 ° C.

  Example 4 Ethyl 2-bromo-4-trifluoromethylbenzoate (Formula IV

  with RI 1 = H, R 2 = CF 3, R 3 = CH 3, R 4 = C 2 H 5).

  In a two-liter flask, 238 g (0.885 mol) of 2-bromo-4-trifluoromethylbenzoic acid are successively introduced into 1000 ml of absolute ethanol and 100 ml of concentrated sulfuric acid.

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  at reflux for 6 hours and then poured, after cooling, on 2.5 liters of ice water; oil formed is extracted with ethyl acetate The organic phase is successively washed with water, 1N sodium hydroxide and again with water After drying over magnesium sulfate, the solvent is evaporated to give 263 g ( yield: 100%) of ethyl 2-bromo-4-trifluoromethylbenzoate in the form of

of a yellow oil.

  EXAMPLE 5 2-Bromo-4-trifluoromethylbenzoic acid (Formula V with R 1 = H, R 2 = CF 3) In a three-liter reactor, 205 g (1 mol) of 4-trifluoromethylanthranilic acid, 600 1 ml of glacial acetic acid and 400 ml of 47% hydrobromic acid After dissolution, the reaction mixture is cooled to -10 ° C. diluted with 400 ml of water and then treated dropwise with a solution of 69 g (1 mol) Sodium nitrite in 200 ml of water while maintaining the temperature below OC When the addition is complete, the reaction mixture is stirred at 0 ° C. for 2 hours. This solution is poured dropwise into a six-liter reactor containing 143.5 g (1 mol) of cuprous bromide in 500 ml of 47% hydrobromic acid maintained at C When the addition is complete, the reaction mixture is stirred at 60 ° C. for one hour, cooled to room temperature and then poured into two liters of ice water The precipitate that form is filtered on sintered glass, washed with water then

  dried under a stream of air 216 g (yield: 80%) of 2-

  bromo-4-trifluoromethylbenzoic acid as a solid melting at 118.5 C.

  The preparation of 4-trifluoromethylanthranilic acid Formula VI

  used in Example 5 is described in the literature.

  Example 6: Second Method: N-ethyl, N-methyl-2- (3,4-

  dimethoxyphenyl) -3,4-dichlorobenzamide (Compound No. 4) (Formula I with R 1 = R 2 = Cl, R 3 = CH 3, R 4 = C 2 H 5) In a 500 ml flask under an inert atmosphere,

  12.4 g (0.040 mol) of N-ethyl, N-methyl-bromide are introduced successively.

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  3,4-dichlorobenzamide, 100 ml of 1,2-dimethoxyethane, 0.5 g of

  tetrakistriphenylphosphine palladium, 8 g (0.044 mol) of 3,4-

  dimethoxyphenylboronic and 60 ml of a 2M aqueous sodium carbonate solution. The reaction mixture is refluxed for 14 hours and then evaporated to a third under reduced pressure. The reaction mixture is poured into two liters of water; the precipitate that forms is filtered on sintered glass, rinsed with water and then dried under a stream of air After purification by chromatography,

  thus obtained 10.3 g (yield: 70%) of N-ethyl, N-methyl-2- (3,4-

  dimethoxyphenyl) -3,4-dichlorobenzamide as a white solid

at 102 C.

  The following compound was prepared in an analogous manner: N, N-diethyl 2- (3,4-dimethoxyphenyl) -3,4-dichlorobenzamide 6.5 g (47.8%) melting at 108 ° C. (Compound No. 5) (Formula I with R 1 = R 2 = C 1, R 3 =

CH 3, R 4 = C 2 H 5).

  Example 7 N-ethyl, N-methyl-2-bromo-3,4-dichlorobenzamide

  (Formula VII with R 1 = R 2 = Cl, R 3 = R 4 = C 2 H 5).

  In a 500 ml flask, 200 ml of

  dichloroethane, 14 g (0.052 mol) of 2-bromo-3,4-dichlorobenzoic acid and 2 ml of N, N-dimethylformamide With stirring and cooling to OC, 11.5 ml of thionyl chloride are then added dropwise. (0.078 mol) When the addition is complete, the reaction mixture is heated gradually to C for 2 hours and then evaporated to dryness. The residue is taken up in 50 ml of tetrahydrofuran and then poured dropwise into a solution containing 13 ml (0, 15 mol) of N-ethyl, N-methylamine in 50 ml of tetrahydrofuran maintained at a temperature below 10 ° C. When the addition is complete, the reaction mixture is stirred at ambient temperature for one hour and then evaporated to dryness. The residue is taken up by dichloromethane, washed successively with 1 N HCl and distilled water After drying over magnesium sulphate, the organic phase is evaporated under reduced pressure to give 12.4 g (yield: 80%) of N-ethyl, N-methyl -2- bromo-3,4-dichlorobenzamide under

  form of a white solid melting at 71 C.

  The following compound was prepared analogously: N, N-diethyl 2-bromo-3,4-dichlorobenzamide (Formula VII with R 1 = R 2 = Cl, R 3 = R 4 = C 2 H 5) 13.6 g (yield: 83.7%). The preparation of 2-bromo-3,4-dichlorobenzoic acid (Formula V with R 1 = R 2 = Cl) used in Example 7 was carried out as above in Example 5: produced in the form of a 63 g beige powder

  (yield: 81%), melting at 196 C.

  EXAMPLE 8 In Vivo Test in a Hothouse Treatment on the Midiou of the Vine (Plasmopara viticola): Vine cuttings (Vitis vinifera) of Chardonnay variety are cultivated in buckets When these plants are 2 months old (stage 8 to 10 leaves, height 20 to 30 cm), they are treated by spray contamination by means of an aqueous suspension of Plasmopara viticola spores, responsible for the downy mildew of the vine, at a rate of approximately 5 ml / plant (approximately 1

x I 05 spores per plant).

  After this contamination, the vine plants are incubated for two days at about 18 ° C. in an atmosphere saturated with moisture, then

  for five days at 20-22 ° C at 90-100% relative humidity.

  The contaminated plants are then sprayed with a suspension or aqueous solution of the test material at the desired concentration and containing a condensate of sorbitan monooleate and 20 oxide molecules.

  half of the active ingredient concentration.

  Each vine plant receives about 5 ml of the solution or dispersion For each concentration of active ingredient to be tested, the treatment is carried out on two plants Contaminated plants, used as controls, are treated with a solution containing no active ingredient, but containing the same condensate

  of sorbitan monooleate and ethylene oxide at the same concentration.

  After drying for 24 hours, the results obtained in the case of the plants treated with the active ingredient to be tested are compared with those obtained in the US Pat.

  case of plants used as a control.

  Under these conditions, it was observed that at the dose of 110 ppm (0.11 g / l) the compounds 1 to 5, resulted in at least 95% inhibition of the development of the fungus, an activity equivalent to that of the commercial reference

  cymoxanyl, taken under the same conditions.

  These examples illustrate the fungicidal properties of the compounds

according to the invention.

  These can indeed be used as fungicidal active ingredients, in particular for the fight against fungal diseases of plants, in particular those caused by pathogenic fungi, particularly those of the family oomycetes of the Phytophthora sp. Type, for example Phytophthora infestans (apple blight). tomato), Phytophthora Citrophthora, Phytophthora capsici Phytophthora cactorumm, Phytophthora palmivora Phytophthora cinnamoni Phytophthora megasperma Phytophthora parasitica, Peronospora (including tobacco mildew), Plasmopara s including Plasmopara viticola (downy mildew) and Plasmopara halstedei (Downy mildew). sunflower), Pseudoperonospora S (including late blight of cucurbitaceae and hops), Bremia lactucae (lettuce bremia), and

soil mushrooms.

  They are advantageously applied at doses of 0.01 to 5 kg / ha, and more

  specifically from about 0.02 to 2 kg / ha.

  For their practical use, the compounds according to the invention are rarely used alone. They are most often part of compositions which can be used for the protection of plants against fungal diseases, or in the compositions regulating plant growth, contain, for example, active ingredient at least one compound according to the invention as described

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  previously in association with solid or inert liquid carriers, acceptable in agriculture and / or surfactants compatible with the active ingredient, also acceptable in agriculture In particular are

  usable inert and usual carriers and the usual surfactants.

  By the term "carrier", in the present description, denotes an organic or inorganic material, natural or synthetic, with which the active ingredient is associated to facilitate its application on the plant, on seeds or on the ground This support is therefore generally inert and must be acceptable in agriculture, in particular on the treated plant The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, fractions of oil, aromatic hydrocarbons

  or paraffinic, chlorinated hydrocarbons, gas.

  The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type. For example, polyacrylic acid salts, lignosulfonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of polyacrylic acid, and ethylene oxide to fatty alcohols or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially

  alkyltaurates), phosphoric esters of alcohols or polyoxyethyl phenols.

  The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and

  that the application vector agent is water.

  The compositions used in the invention may be under

  quite diverse forms, fluid, liquid, or solid.

  As forms of fluid or liquid compositions, mention may in particular be made of emulsifiable concentrates, emulsions, concentrated aqueous suspensions, pastes, solutions, in particular concentrates which are soluble in water, solutions concentrated in an organic medium,

(ULV solution) and aerosols.

  The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active material In addition to the active ingredient and the solvent, the Emulsifiable concentrates may contain, when necessary, a suitable co-solvent and from 2 to 20% of appropriate additives, such as stabilizers, penetration agents,

  corrosion, dyes, adhesives.

  From these concentrates, it is possible to obtain by dilution with water emulsions of any desired concentration, which are particularly suitable for

application on crops.

  As examples, here is the composition of some emulsifiable concentrates:

Example CE 1:

  active ingredient (Compound No. 1) 250 g / 1 epoxidized vegetable oil 25 g / l mixture of alkylaryl sulfonate and polyglycol ether and fatty alcohols 100 g / l dimethylformamide 50 g / 1 xylene 575 g / l

Example CE 2:

  active ingredient (compound 2) 400 g / l alkaline dodecylbenzene sulfonate 24 g / l nonylphenol oxyethyl 10 ethylene oxide molecules 16 g / l cyclohexanone 200 g / l aromatic solvent qs 1 1

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  From these concentrates, it is possible to obtain by dilution with water emulsions of any desired concentration, which are particularly suitable for

the application on the leaves.

  The concentrated suspensions, also applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0 to 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or mineral salts may be dissolved in the support to help prevent sedimentation or as antifreezes for water. By way of example, here is the composition of several concentrated aqueous suspensions according to the invention:

Example SAC 1:

  An aqueous suspension is prepared comprising: active ingredient (compound 3) wetting agent (polyethoxylated alkylphenol) dispersing agent (Na naphthalene sulphonate) antifreeze (Propylene glycol) thickener (polysaccharide) biocide (formaldehyde) water g / g / 1 lg / lg / l 3 g / 1 lg / l QS P 1 liter

Example SAC 2:

  An aqueous suspension is prepared comprising: active ingredient (Compound No. 4) 250 g / 1 wetting agent (polyethoxylated C 13 synthetic alcohol): 10 g / l dispersing agent (sodium lignosulfonate) 15 g / l antifreeze (urea) 50 g / 1 thickener (Polysaccharide) 2.5 g / 1 biocide (formaldehyde) 1 g / l water QSP 1 liter

Example SAC 3:

  An aqueous suspension is prepared comprising: active ingredient (compound No. 5) 500 g / l wetting agent (synthetic polyethoxylated C 13 alcohol): 10 g / 1 dispersing agent (ethoxylated polyarylphenol phosphate salified) g / I antifreeze (propylene glycol) 100 g / l thick (polysaccharide) 1.6 g / l biocide (sodium methylhydroxy-4-benzoate) 3.3 g / l

water Q S P 1 liter.

  As forms of solid compositions, mention may be made of dusting powders (with an active material content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound of formula (I) in these granules being between 0.5 and 80% for

these latter cases).

  Wettable powders (or powders for spraying) are usually prepared to contain 10 to 95% active ingredient, and usually contain, in addition to the solid support, from 0 to 5% wetting agent, at 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc. As an example, here is the weight composition of several powders

wettable.

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Example PM 1:

  active ingredient (Compound No. 1) 10% ethoxylated branched ethoxylated ethoxylated C 13 ethoxylated alcohol with 8 to 10 ethylene oxide (wetting agent) 0.75% neutral calcium lignosulfonate (dispersing agent 12%

  calcium carbonate (inert filler) qs 100%.

Example PM 2:

  active ingredient (compound 2) 50% ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated styrylphenol (dispersing agent) 5% chalk (inert carrier) 42.5% Example PM 3: the same ingredients are used as in previous example, in the following proportions: active ingredient (compound 2) 75% wetting agent 1.5% dispersing agent 8% calcium carbonate (inert filler) qs 100%

Example PM 4:

  active ingredient (compound 3) 90% ethoxylated fatty alcohol (wetting agent) 4% ethoxylated styrylphenol (dispersing agent) 6% To obtain these wettable powders or wettable powders, the active ingredient is intimately mixed in suitable mixers with the additional substances and grinding with mills or other suitable grinders. Thereby obtainable powders, whose wettability and

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  suspending are advantageous; they can be suspended with water at any desired concentration and this suspension can be used very

  advantageously in particular for application to the leaves of plants.

  The compounds of formula (I) can still be used in the form of dusting powders; a composition comprising 50 g of active material and 950 g of talc can also be used; a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc can also be used; these constituents are mixed and milled and the mixture is applied by dusting. The granules for dusting have dimensions of between 0.1 and 2 mm and can be manufactured by agglomeration or impregnation In general, the granules contain 0.5 to 25% of active material and 0 to 10% of additives such as stabilizers, slow release modifiers, binders

and solvents.

  Here are two examples of granule composition: Examples G 1 and G 2: active ingredient (compound NO 4 50 g 200 g propylene glycol 50 g 50 g cetyl and polyglycol ether 2.5 g 2.5 g polyethylene glycol 35 g g

  kaolin (particle size: 0.3 to 0.8 mm) 910 g 760 g.

  The compounds according to the invention can be advantageously formulated in the form of water-dispersible granules which are also included

in the context of the invention.

  These dispersible granules, whose bulk density is generally between approximately 0.3 and 0.6, have a particle size generally of between approximately 150 and 2000, and preferably between 300 and 1500,

microns.

  The active ingredient content of these granules is generally

  between about 1% and 90% and preferably between 25% and 90%.

  The rest of the granule is essentially composed of a solid filler and optionally surfactant adjuvants conferring on the granule properties of dispersibility in water These granules can be essentially of two distinct types depending on whether the filler is water-soluble, it can be mineral and preferably organic Excellent results have been obtained with urea In the case of an insoluble filler, it is preferably mineral, such as kaolin or bentonite It is then accompanied by surfactants active agents (in a proportion of 2 to 20% by weight of the granule), surfactant adjuvants of which more than half is composed of at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth poly (naphthalene sufonate) or an alkaline or alkaline-earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as

alkyl-

  alkaline or alkaline earth naphthalene sulphonate.

  Moreover, although this is not essential, we can

  add other adjuvants such as antifoam agents.

  The granulate according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (dredger, fluid bed, atomizer, extrusion, etc.) It usually ends with crushing followed by sieving to the particle size

  chosen within the limits mentioned above.

  Preferably, it is obtained by extrusion. Working as indicated in the examples below, the following compositions of

dispersible granules.

Example GD 1:

  In a mixer, 90% by weight of active ingredient (NO 5 compound) and 10% of bead urea are mixed. The mixture is then milled in a pin mill. A wet powder is obtained and extruded in a perforated roll extruder. gets a granule that is dried, then crushed and sieved, so as to keep only granules of one dimension

between 150 and 2000 microns.

  Example GD 2: In a mixer, the following constituents are mixed: active ingredient (compound n 2) 75% wetting agent (sodium alkylnaphthalene sulphonate 2% dispersing agent (sodium polynaphthalene sulphonate 8% inert load insoluble in water (kaolin ) 15%

Example GD 3:

  active ingredient (compound 1) 20% sodium alkylnaphthalene sulphonate 2% sodium methylene bis naphthalene sulphonate 8% 70% kaolin This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved in order to obtain granules of dimension

between 0.16 and 0.40 mm.

  These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active ingredients, in particular fungicides, the latter being in the form of powders. wettable, or

aqueous granules or suspensions.

  The compounds according to the invention may also be formulated in the form of organic solutions which may be encapsulated, in particular by interfacial polymerization, in capsules with a polymeric wall, for example based on polyamides of polyurea or polyamide ureas. These capsules are in the form of concentrated aqueous dispersion that one can

  dilute at the time of use to obtain a spray mixture.

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  As already mentioned, aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included

  in the general context of the compositions that can be used in the present invention.

  The emulsions can be of the water-in-oil or oil-in-water type and they

  may have a thick consistency like that of a "mayonnaise".

  The invention further relates to a method of treatment, both in curative and preventive, plants against diseases caused by phytopathogenic fungi including those of the family oomycetes type Phvtophthora sp eg Phytophthora infestans (apple blight)

  ground or tomato), Phytophthora Citrophthora Phytophthora capsici.

  Phytophthora cactorum, Phytophthora palmivora, Phytophthora cinnamoni ,.

  Phytophthora megasperma, Phytophthora parasitica Peronospora 2 (including tobacco mildew), Plasmopara sp including Plasmopara viticola (grape mildew) and Plasmopara halstedei (sunflower mildew), Pseudoperonospora S 2 (including late blight of cucurbitaceae and hops), Bremia lactucae ( Bremia lettuce), as well as soil fungi, this

  process being characterized in that a derivative according to the invention is applied.

  The excellent curative activity of the compounds according to the invention is particularly advantageous since it makes it possible to reduce the number of preventive treatments.

  while ensuring good pest control.

  These derivatives can be used as the only active ingredient or in combination with another agrochemical active ingredient, especially a fungicidal agent such as, for example, those of the family of thiocarbamates, ethylene bis (dithiocarbamates), such as thiram, maneb, zineb and mancozeb, phthalimides, such as captan, captafol and folpet, acylalanines, such as metalaxyl, oxadixy I and benalaxyl, copper-based compounds, phosphorous acid derivatives such as phosethyl- Go

  dithianon, chlorothalonil, cymoxanyl, thiadiazoles, N, N'dialcoyl-

N-phénylsulfamides.

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  This process is characterized in that it consists in applying to these plants an effective amount of a composition containing as active ingredient a compound according to formula (1). "Effective amount" means an amount sufficient to allow the control and destruction of fungi present on these plants the use rates may however vary within wide limits depending on the fungus to be fished, the type of crop, the conditions

  climatic conditions, and according to the compound used.

  In practice, doses ranging from 1 g / hl to 500 g / hl substantially corresponding to doses of active ingredient per hectare of 10 g / ha to 5000 g / ha

  about usually give good results.

  Examples of useful treatment methods include foliar or ground spraying, dusting, dipping, incorporation of granules, powders or slurries, watering, injection into the soil,

  trees, brushing and seed treatment.

Claims (9)

  1) Compound of formula (1): R 2 in which: R 1 and R 2, identical or different, are a hydrogen or halogen atom or an optionally halogenated alkyl radical, and -R 3 and R 4, identical or different, are alkyl of 1 to 4 carbon atoms or can form, together with the nitrogen atom which carries them, a morpholino cycle.   2) A compound according to claim 1, characterized in that, in formula I, R 1 and R 2, which are identical or different, are a hydrogen atom or a   chlorine or a trifluoromethyl group.   3) A compound according to claim 1, characterized in that, in the formula, one of R 1, R 2 is a hydrogen atom and the other is the trifluoromethyl group. 4) Compound according to claim 1, characterized in that, in the   formula, R 1, R 2 are each a chlorine atom.   OCH 3 OCH 3) Compound according to claim 1, characterized in that, in the   Formula I, R 3 and R 4, which may be identical or different, are a methyl or an ethyl.   6) Compound according to claim 1, characterized in that, in formula I, R 3 and R 4 form, together with the nitrogen atom which carries them, a morpholino cycle.   7) Fungicidal composition for the protection of plants, characterized in that it contains, as active ingredient, a compound according to one of the Claims I to 6.   8) Process for the protection of plants against fungal diseases,   characterized in that a compound according to one of claims 1 to   6. 9) Method according to claim 8, characterized in that a cure.   ) Process for the preparation of the compounds of formula (1), according to one   Claims 1 to 7, characterized in that compounds of formula   (lu): R 2 OCH 3 OCH 3 in which R 1 and R 2 have the same meaning as in formula I, by an activating agent for their acid function and in that the product obtained is reacted with an HNR amine 1 R 2, in the presence of an organic base or   mineral in an organic solvent.   11) Process according to Claim 10, characterized in that the activating agent for the acid function is chosen from the group comprising thionyl chloride (SOC 12), phosphoryl chloride (POC 13), trichloride or pentachloride phosphorus (PC 13, PC 15), dicyclohexylcarbodiimide, diimidazole carbonyl, alkyl chloroformates and trifluoroacetic anhydride, and in that the reaction with the amine HNR 1 R 2 is carried out in a solvent selected from the group consisting of chlorinated solvents or   aromatics and ethers such as THF.   12) Process for the preparation of the compounds of formula (II) according to claim 10, characterized in that saponifies compounds of formula (m): R 2 OCHC 3 R 1 OCH 3   in which R 1 and R 2 have the same meaning as in formula I and R is an alkyl of 1 to 4 carbon atoms, in an alcohol such as ethanol in the presence of water and a base alkaline mineral, at a temperature between room temperature and the reflux of the reaction mixture, the reaction mixture being subsequently treated with   an organic or inorganic acid such as hydrochloric acid.   Ip Aq Al PAR 13) Process for the preparation of the compounds of formula (III) according to claim 12, characterized in that an aryl coupling reaction is carried out between a compound of formula (IV): OR R 2 / Br R 1 in which R, R 1 and R 2 have the same meaning as in formula III and none of the substituents R 1, R 2 can be simultaneously a bromine or iodine atom,   and 3,4-dimethoxyphenylboronic acid in the presence of a catalyst.   14) Process for the preparation of the compounds of formula (1), characterized in that an aryl coupling reaction is carried out between a compound of formula (VI): NR 3 R 4   R 2 Br R 1 in which R 1 and R 2 have the same meaning as in the formula Im and can not be simultaneously a bromine or iodine atom,   and 3,4-dimethoxyphenylboronic acid, in the presence of a catalyst.   Process for the preparation of compounds of formula VII, characterized in that compounds of formula (V): OH in which R 1 and R 2 have the same meaning as in formula I, are treated with an activating agent for their function acid and in that the product obtained is reacted with an amine HNR 1 R 2 in the presence of an organic base or   mineral in an organic solvent. t